WO2000031188A1 - Use of compositions containing bisazo compounds for detecting fissures - Google Patents

Abstract

The invention relates to the use of compositions which contain as components: A) at least one bisazo compound selected from the group consisting of the compounds of general formula (Ia), and general formula (Ib) wherein R<1> is C1-C8 alkyl, R<2> is C2-C8 alkyl, R<3>, R<3'> is C2-C21 alkyl, wherein up to four CH2 groups of the carbon chain can be substituted by oxygen in the ether function, R<4> is hydrogen or may independently of R<3> have the meaning of R<3>, R<4'> is hydrogen or may independently of R<3'> have the meaning of R<3'>; B) at least one solvent in which component A) is soluble and optionally C) at least one surface-active substance. Said compositions are used as fissure-detection agent for detecting surface fissures or other defects in work pieces to be examined. The invention further relates to compositions containing the above-mentioned components A), B) and C).

Description

Use of compositions containing bisazo compounds as crack detection agents

description

The present invention relates to the use of compositions which contain as components

A) at least one bisazo compound selected from the group consisting of the compounds of the general formula Ia

and the general formula Ib

in which mean

R ¹ -C ₈ alkyl,

R ² C ₂ -C ₈ alkyl,

R ³ , R ³ 'C -C ₂ Alkyl-alkyl, in which up to four CH groups of the carbon chain can be replaced by oxygen in ether function,

R ^{4 is} hydrogen or, independently of R ^3, the meaning of R ³ ,

R ⁴ 'is hydrogen or, independently of R ³ ', the meaning of R ³ ', B) at least one solvent in which component A) is soluble and optionally

C) at least one surface-active substance,

as a crack detection device for the detection of superficial cracks or other defects in workpieces to be examined in this regard.

The invention further relates to compositions which contain the above-mentioned components A), B) and C).

US Pat. No. 4,191,048 describes a method for the detection of cracks and other defects in workpieces. A composition which contains a solution of an isomer mixture of a red bisazo dye which is visible in daylight and a surface-active substance which is miscible with this solution is used as the crack testing agent. This mixture of isomers of the red bisazo dye is derived from the (statistically) methyl-substituted aminoazobenzene (as starting material for the diazo component) and a Cs -C -alkyl -ß-naphthol or mixtures of such Cs-Cι ₂ - alkyl-ß-naphthols (as a coupling component).

This dye (or the mixture of isomers of this dye) clearly marks the cracks in the workpiece to be tested, but it is disadvantageous that it contains toxic, isomeric bisazo compounds.

The German laid-open specification DE-A 35 07 174 describes a method for documenting crack tests on workpieces, according to which dyes or dye precursors are used which pass from the cracks in the workpiece to a flat substrate brought into contact with the workpiece. According to this document, such a substrate is preferably paper, which can optionally also be provided with a receiver layer.

Solvent Yellow 56 (C.I. 11021), Solvent Yellow 14 (C.I. 12055), Dispers Red 1 (C.I 11110), Dispers Blue 3 (C.I. 61505) and Solvent Orange 3 (C.I 11270) are described as suitable dyes.

The oil-soluble yellow and orange (“solvent”) dyes mentioned generally show too little contrast to the color of the workpiece due to their light color; the dispersion (“dispers”) dyes mentioned are in turn in the solvent of the crack detection agent not sufficiently soluble, so that due to the insufficient dye concentration results in an insufficient contrast to the color of the workpiece.

It was therefore an object of the present invention to provide a crack detection agent which permits high-contrast marking and whose dye (s) are not based on amines of class III A 2 - as in TRGK (Technical Rules for Hazardous Substances) 614 defined- based.

This object was achieved by using the compositions described at the outset as crack testing agents for the detection of superficial cracks or superficial other defects in workpieces to be examined in this regard.

As C ₂ -C ₈ alkyl for R ² are both unbranched alkyl chains, such as ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, n-pentyl, pent-2-yl, pent-3- yl, n-hexyl, hex-2-yl, hex-3-yl, n-heptyl, hept-2-yl, hept-3-yl, hept-4-yl, n-octyl, oct-2-yl, Oct-3-yl and oct-4-yl as well as branched alkyl chains, such as i-butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1,1-dimethylpropyl, 1, 2 -dimethylpropyl, 2-methylpentyl, 3 -methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2 -dimethylbutyl, 1,3-dryness -thylbutyl, 2, 2 -dimethylbutyl, 2, 3 -dimethylbutyl, 3, 3 -dimethylbutyl, 2 -ethylbutyl, 1, 1, 2 -trimethylpropyl, 1, 2, 2 -trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl and 2-ethylhexyl in question.

As C ₁ -C ₈ alkyl for R ¹ , in addition to the radicals mentioned above, methyl is also suitable.

As C ₂ -C ₂ -alkyl for R ³ and R ⁴ or R ³ 'and R ⁴ ', in each case independently of one another, in addition to the unbranched or branched C -C -alkyl radicals already mentioned as examples under R ² , both the unbranched C ₉ - C ₂ ι-alkyl radicals, such as n-nonyl, n-decyl, n-ündecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n- Nonadecyl, n-eicosyl or n-heneicosyl and the corresponding residues which are isomeric with regard to their attachment (yl position) as well as the corresponding branched C ₉ -C ₂ -alkyl residues in question.

For R ³ and R ⁴ or R ³ 'and R ⁴ ', C ₂ -C ₂ Alkyl-alkyl, in which up to four CH ₂ groups of the carbon chain can be replaced by oxygen in ether function, are suitable, for example 2 -Methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2 - or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 2- or 4-butoxybutyl, 3, 6-dioxaheptyl, 3, 6-dioxaoctyl, 4, 8-dioxanonyl, 3, 7-dioxaoctyl, 3, 7-dioxanonyl, 4, 7-dioxaoctyl, 4, 7-dioxanonyl, 4, 8-dioxadecyl, 3, 6, 8-trioxadecyl, 3, 6, 9-trioxaundecyl, 3, 6,, 12-tetraoxatride-cyl, 3,6,9, 12-tetraoxatetradecyl.

Further such residues are oligopropylene glycol groups, which are derived from the addition of one, two, three or four propylene oxide molecules per amino group of the naphthylamine, and their methyl or ethyl ether.

Such radicals correspond, for example, to the formulas - (0-CH ₂ -CH ₂ (CH ₃ ) -) _n -OR or - (0-CH ₂ (CH ₃ ) -CH ₂ -) _n -OR, in which n values of 1 , 2, 3 or 4 and R represents hydrogen, methyl or ethyl.

Compositions are preferably used in which R ¹ and R ^{2 represent} the Cχ-C or C ₂ -C ₄ -alkyl radicals already exemplified above.

As C ₂ -C ₂₁ alkyl for R ⁴ and / or R ³ or R ⁴ 'and / or R ³ ', in particular 2-ethylhexyl and unbranched or branched tride- cyl may be mentioned.

Compositions in which component A) consists of at least one bisazo compound of the formula Ia are particularly preferably used. The preferences already mentioned also relate to the composition mentioned here which is to be used with particular preference.

The bisazo compounds of the formulas Ia and Ib are usually prepared in two reaction steps. By azo coupling of the diazo compound obtained from the meta-R ¹ -aminobenzene (<Kχ)) or ortho-R ² -aminobenzene ((K ₂ )) with another molecule of the corresponding amine, the substituted azobenzene ("di- (Kχ) "or" Di- (K ₂ ) ") obtained. This is again diazotized and in the second step with a molecule of R ³ , R ⁴ - or R ³ ', R ⁴ ' - (di) substituted naphthylamine (coupling component (K ₃ ) or (K ₃ ')) implemented to the corresponding target compound of the formula la or Ib. The following reaction scheme illustrates this again by way of example for the preparation of bisazo compounds of the formula Ia.

(Kx) "Di (Kχ)

This scheme applies analogously to the preparation of the compounds of the formula Ib.

Such compounds to be used in accordance with the invention are produced e.g. based on the explanations in the specification DE 24 13 369 B2 and the published patent application DT 23 61 758 AI and is therefore not a problem for the person skilled in the art.

The alkyl radicals R ¹ or R ^{2 of} the aromatic amine components (Ki) or (K) are mostly defined radicals, ie the amine components (Ki) or (K ₂ ) are generally pure compounds.

The radicals R ³ and / or R ⁴ or R ³ 'and / or R ⁴ ' of the coupling component (K ₃ ) or (K ₃ '), however, denote, especially in the case of higher alkyl radicals, in which up to four CH ₂ groups of the carbon chain can be replaced by oxygen in ether function, often mixtures of several isomeric alkyl radicals, so that the (di) substituted naphthylamines (K ₃ ) or (K ₃ ') are representative of isomer mixtures with regard to these in the given case Leftovers stand.

This is mostly due to the preparation of such (di) substituted naphthylamines, since these are usually prepared starting from naphthylamine and reactants which contain mixtures of isomers of such alkyl radicals. Isomer mixtures of alkyl halides or also of epoxides are generally used as such reactants. In this sense, the formulas Ia and Ib in the given case also stand for isomer mixtures of bisazo compounds with regard to the radicals R ³ and / or R ⁴ or R ³ 'and / or R ⁴ '.

Furthermore, the above-mentioned amine components (Ki) or (K ₂ ) and the bisazo compounds to be used according to the invention do not fall under TRGS 614 and are therefore not subject to the restrictions of use specified therein. This aspect has already been discussed at the beginning.

Possible solvents (component B)) for component A) are:

-C-C alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, and in particular the C ₅ -C ₂ alcohols n-pentanol, n-hexanol, n-heptanol, n Octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol and their isomers,

Glycols, e.g. 1,2-ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 2,3- or 1,4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol,

Ethers such as Methyl tert-butyl ether, 1,2-ethylene glycol mono- or dimethyl ether, 1,2-ethylene glycol mono- or diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran or dioxane,

Ketones, e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone or diacetone alcohol (4-hydroxy-4-methyl-2-pentanone),

C 1 -C ₅ -alkyl esters, such as, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate or amyl acetate,

aliphatic or aromatic hydrocarbons such as e.g. Pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white spirit, Shellsol® or Solvesso®

Mineral oils, e.g. Petrol, kerosene, diesel oil or heating oil,

but also natural oils, e.g. Olive oil, soybean oil, rapeseed oil or sunflower oil.

Mixtures of these solvents are of course also suitable as component B). The compositions to be used as crack testing agents according to the invention can additionally also contain surface-active substances (component C)).

These substances can be both cationic, anionic, nonionic and zwitterionic compounds or mixtures of such compounds.

You can e.g. - Without being assigned to one of these classes by the order of the following performance - Polycarboxylates and copolymers, which are sold under the brand names Sokalan® or Elvacite®, or so-called "Hyperdispersants", which are sold under the name Solsperse® Add formaldehyde condensates based on aromatic sulfonates or alkylaromatic sulfonates, which are available under the brand names Tamol® and Nekal® as well as Supragil® and Rhodacar®.

You can also use it, for example

Alkoxylation products based on aliphatic or alkyl aromatic hydroxy, amino and aminohydroxy compounds and under the brand names Synperonic® and Ukanil®, Dehypon®, Neopol® ethoxylates, Emulan®, Lutensol®, Plurafac® and Pluronic® or Elfapur® are commercially available,

Polyalkylene glycols, known under the brand names Pluriol® and Antarox®, and their alkyl ethers,

aliphatic and alkyl aromatic single and multiple sulfonates with the brand names Lutensit®, Rhodacar®, Rhodapon® and Teepol®,

Acid esters and amides such as B. sulfosuccinic acid ester of the brand Elfanol®,

Phosphoric acid partial esters, which are sold under the names Rhodafac® or Marlophor®,

Fatty acid partial glycerides and fatty acid alkanolamides, which can be obtained under the brand names Luwitor® or Marlamid®,

as well as the surfactants offered under the names Plantaren® and Glucopon®. Furthermore, surface-active substances with betaine or sultain groups can also be used, which are inner salts of quaternary ammonium and carboxylate (betaine) or sulfonate (sultain) ions and z. B. are available under the brand names Mackam®. Cationic surface-active substances based on quaternary ammonium compounds and amine oxides, such as those offered under the names Alkaquat® and Rhodaquat® as well as Mackalene®, Mackernium®, Mackpro® and Mackamine®, can also be used.

In the event that the addition of surface-active substances (component C)) to the compositions is desired, nonionic or anionic surfactants are preferably added. Alkoxylation products based on aliphatic or alkyl aromatic hydroxy, amino and aminohydroxy compounds, polyalkylene glycols and their alkyl ethers and formaldehyde condensates based on aromatic sulfonates or alkyl aromatic sulfonates are particularly suitable here.

The present invention further relates to compositions which contain components

A) at least one bisazo compound selected from the group consisting of the compounds of the formulas Ia and Ib mentioned at the outset,

B) at least one solvent in which component A) is soluble and

C) at least one surface-active substance.

These compositions preferably contain bisazo compounds of the formulas Ia and Ib, in which R ^{1 is} C ₁ -C ₄ -alkyl and R ^{2 is} C ₂ -C -alkyl. These preferred alkyl radicals have already been listed as examples above.

Compositions in which component A) consists of at least one bisazo compound of the formula Ia are particularly preferred. The preferences already mentioned also relate to the particularly preferred composition mentioned here.

Examples of solvents (component B)) in the compositions according to the invention have already been listed as examples above. Examples of surface-active substances (component C)) in the compositions according to the invention have likewise already been listed as examples above.

Compositions are preferred in which component C) consists of at least one nonionic or anionic surface-active substance. In particular, the nonionic surface-active substance is concerned

Alkoxylation products based on aliphatic or alkyl aromatic hydroxy, amine and aminohydroxy compounds and under the brand names Synperonic® and ükanil®, Dehypon®, Neopol® ethoxylates, Emulan®, Lutensol®, Plurafac® and Pluronic® or Elfapur® are commercially available,

Polyalkylene glycols and their alkyl ethers known under the brand names Pluriol® and Antarox®,

Acid esters and amides, such as. B. sulfosuccinic acid ester of the brand Elfanol®,

Fatty acid partial glycerides and fatty acid alkanolamides, which can be obtained under the brand names Luwitor® or Marlamid®,

as well as the products offered under the Plantaren® and Glucopon® names.

The anionic surface-active substance is, in particular, formaldehyde condensates based on aromatic sulfonates or alkylaromatic sulfonates, which are available under the brand names Tamol® and Nekal® as well as Supragil® and Rhodacar®.

The preferences described above with regard to the bisazo compounds and their preferred substituents also apply to such preferred compositions (containing nonionic or anionic surface-active substances).

Compositions and their preferred embodiments are particularly preferred in which component C) consists of the alkoxylation product or a mixture of alkoxylation products of aliphatic or alkylaromatic hydroxyl, amino or hydroxyamino compounds.

These alkoxylation products are usually based on ethylene oxide, propylene oxide or mixtures of these alkylene oxides as alkoxylation agents. The aliphatic or alkyl aromatic Hydroxy, amino or hydroxyamino compounds form the

"Head unit", at whose hydroxy, amino or hydroxyamino functionalities the oligomerization / polymerization ("tail") of the

Ethylene oxide, propylene oxide or mixtures of these alkylene oxides begins. In addition, free hydroxy groups can

Alkyl groups must be etherified.

The "head units" are usually fatty alcohols (linear, saturated or unsaturated primary C ₆ -C alcohols), oligosaccharides, alkylphenols, fatty amines (linear, saturated or unsaturated mostly primary C ₆ -C ₂₂ amines) and low molecular weight addition products from simple or multiple amines and alkylene oxides (hydroxyamines).

The fatty alcohol and alkylphenol alkoxylates include, for example, the products commercially available under the Lutensol®, Plurafac® and Pluronic® brand names. Furthermore, reference is expressly made here to the nonionic surface-active substances with comparable chemistries, which are described in US Pat. No. 4,191,048 in the text passage beginning with column 4, line 52 and ending with column 8, line 30 and which are described here as by Reference should apply incorporated.

Compositions and their preferred embodiments in which component C) consists of a polyalkylene glycol, a polyalkylene glycol alkyl ether or a mixture of polyalkylene glycols and / or polyalkylene glycol alkyl ethers among one another or with one another are also particularly preferred.

For example, the polyalkylene glycols commercially available under the brand names Pluriol® and Antarox® may be mentioned here.

The compositions to be used according to the invention contain component A) in a proportion of 0.10 to 25.0% by weight, preferably in a proportion of 1.0 to 10.0% by weight and accordingly component B) in a proportion of 75.0 to 99.90% by weight, preferably in a proportion of 90.0 to 99.0% by weight, based on the total amount of component A) and component B).

If component C) is present, its proportion is 1.0 to 15.0% by weight, preferably 2.0 to 5.0% by weight, of the total amount of components A), B) and C). The total amount of components A) and B) adds up to 100% by weight and is accordingly 85.0 to 99.0% by weight, preferably 98.0 to 95.0% by weight. The Ver- Ratio of component A) to component B] is derived from the information previously given.

Component C) is in the compositions according to the invention in a proportion of 1.0 to 15.0% by weight, preferably 2.0 to 5.0% by weight, based on the total amount of components A), B) and C. ) , contain. The total amount of components A) and B) adds up to 100% by weight and is accordingly 85.0 to 99.0% by weight, preferably 98.0 to 95.0% by weight. The ratio of components A) and B) to each other is again based on the information previously given.

The procedures for using crack testing agents are familiar to the person skilled in the art and e.g. described in detail in DIN 54 152, German Offenlegungsschrift DE-A 35 07 174 and in US Pat. No. 4,191,048, so that there is no need to go into this here.

Examples: dyes

The following dyes were synthesized using customary methods:

Farbstoff Struktur

Dye structure

In the dyes of Examples 2 and 4, the "i-tridecyl" radical is understood to mean a mixture of the isomeric C ₃ H radicals.

Examples: compositions

The following table shows examples of compositions that are well suited as crack testing agents. They are obtained by mixing the individual components. The percentages are% by weight. Shellsol ^® AB is a high-boiling aromatic mixture (commercially available from Shell).

Beispiel Zusammensetzung

Example composition

29 5% dye 2

93% ethyl acetate

2% Nekal ^® BX

30 5% dye 2 28% Shellsol ^® AB 65% ethyl acetate

2% Nekal ^® BX

31 1% dye 3 99% Shellsol ^® AB

32 2% dye 3 98% Shellsol ^® AB

33 5% dye 3 95% Shellsol ^® AB

34 5% dye 3 93% Shellsol ^® AB 2% Nekal ^® BX

35 5% dye 3 28% Shellsol ^® AB 65% ethyl acetate

Claims

claims 1. Use of compositions containing as components A) at least one bisazo compound selected from the group consisting of the compounds of the general formula Ia

in which mean R ¹ -C ₈ alkyl, R ² C ₂ -C ₈ alkyl, R ³ , R ³ 'C ₂ -C 1 -alkyl, in which up to four CH ₂ groups of the carbon chain can be replaced by oxygen in ether function, R ^{4 is} hydrogen or, independently of R ^3, the meaning of R ³ , R ⁴ 'is hydrogen or, independently of R ³ ', the meaning of R ³ ', B) at least one solvent in which component A) is soluble and optionally C) at least one surface-active substance, as a crack detection device for the detection of superficial cracks or other defects in workpieces to be examined in this regard. 2. Use of compositions according to claim 1, in which R ¹ in the bisazo compounds of the formulas Ia C ₁ -C ₄ alkyl and R ² in the bisazo compounds of the formulas Ib is C ₂ -C ₄ alkyl. 3. Use of compositions according to Claim 1 or 2, in which component A) consists of at least one bisazo compound of the formula Ia. 4. Use of compositions according to claims 1 to 3, in which the optional component C) consists of at least one nonionic or anionic surface-active substance. 5. Compositions containing as components A) at least one bisazo compound selected from the group consisting of the compounds of the formulas Ia and Ib according to claim 1, B) at least one solvent in which component A) is soluble and C) at least one surface-active substance. 6. Compositions according to claim 6, in which R ¹ in the bisazo compounds of the formula Ia is C ₁ -C ₄ alkyl and R ² in the bisazo compounds of the formulas Ib is C ₂ -C ₄ alkyl. 7. Compositions according to claim 5 or 6, in which component A) consists of at least one bisazo compound of the formula la. 8. Compositions according to claims 5 to 7, in which component C) consists of at least one nonionic or anionic surface-active substance. 9. Compositions according to claims 5 to 7, in which component C) consists of the alkoxylation product or a mixture of alkoxylation products of aliphatic or alkyl-aromatic hydroxy, amino or aminohydroxy compounds. 10. Compositions according to claims 5 to 7, in which the Component C) consists of a polyalkylene glycol, a polyalkylene glycol alkyl ether or a mixture of polyalkylene glycols and / or polyalkylene glycol alkyl ethers with one another or with one another.